145 



AcYL Derivatives of 0-Aminophenol. 



J. H. Ransom and R. E. Nelson. 



In an extended piece of work published some years ago the senior author 

 (Amer. Chern. Journ., 23, 1) foimd that when o-nitro phenylethylcarbonate 

 was reduced with tin and hydrochloric acid a urethane was obtained, soluble 

 in alkalis and evidently having the carbethoxy group attached to nitrogen. 

 By modifying the conditions he was able to isolate an isomeric basic material 

 in which the carbethoxy group was attached to oxygen. On standing this 

 rapidly changed to the urethane. The same urethane was obtained on treat- 

 ing o-aminophenol, in ether solution, with chlorcarbonicethylether. A similar 

 rearrangement occurs when o-nitro phenylbenzoate is reduced in acid solution 

 (Bottscher, Ann. Chem. Pharm., 210, 384). In determining the constitution 

 of the oxyphenyl urethane Ransom made the diacyl derivative by using ben- 

 zoyl chloride in alkaline solution. He also found that the same substance 

 was produced when Bottscher' s benzoyl o-aminophenol was treated with chlor- 

 carbonicethylether in alkaline solution. In both cases saponification gave 

 benzoic acid and oxyphenylure thane, indicating that in the latter case a 

 molecular rearrangement of the diacyl derivative had occurred, so as to leave 

 the lighter group attached to nitrogen. Other diacyl derivatives of o-amino- 

 phenol were made and in every case the lighter group was found attached to 

 the amide nitrogen. If one of the amide hydrogens is first replaced by a 

 hydrocarbon radical no rearrangement occurs, but isomeric substances are 

 formed when the acyl groups are introduced in reverse order. The same is 

 true when the amide and hydroxyl groups are in the meta or para position to 

 each other. 



It seemed desirable to determine whether the carboxylester group would 

 become attached to nitrogen in the presence of a carbonyl group already 

 attached to the same nitrogen; also whether of two carboxyl groups intro- 

 duced the lighter one would go to the nitrogen. Finally it seemed of interest 

 to determine if rearrangement would occur in case the radicals introduced 

 were nearly of the same weight. If the rearrangement did not occur or pro- 

 ceeded more slowly than the others it was thought there would be a chance 

 of studying more thoroughly the mechanism of the rearrangement. 

 10—1019 



